US4237302A - Dichloroacetylimino herbicide antagonists as plant protection agents - Google Patents
Dichloroacetylimino herbicide antagonists as plant protection agents Download PDFInfo
- Publication number
- US4237302A US4237302A US05/946,975 US94697578A US4237302A US 4237302 A US4237302 A US 4237302A US 94697578 A US94697578 A US 94697578A US 4237302 A US4237302 A US 4237302A
- Authority
- US
- United States
- Prior art keywords
- soil
- corn
- herbicide
- antagonist
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
- C07D285/135—Nitrogen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/38—Nitrogen atoms
- C07D277/40—Unsubstituted amino or imino radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/38—Nitrogen atoms
- C07D277/44—Acylated amino or imino radicals
- C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
Definitions
- Amides of dichloroacetic acid derived from a large number of amines are known to be useful as herbicide antagonists to protect plants from pre-emergent thiocarbamate herbicides, as disclosed in U.S. Pat. Nos. 4,021,224 and 4,033,756.
- Plant protecting antagonists have been used commercially in two ways, (1) by application to the crop seeds at, or prior to planting, so as to assure that antagonist is present when the seeds germinate and begin to grow, or (2) by application to the soil, so that if pre-emergent herbicide in the soil reaches the crop seeds, the antagonist will also be present and will protect the germinating and growing plants.
- the second method is not as controllable as the first method.
- Diffusion of the antagonist in the soil may be at a different rate from the diffusion rate of the herbicide and the difference may be dependent upon weather and soil type.
- Direct seed treatment is generally more effective and efficient with respect to the use of chemicals.
- application to the soil is very convenient and requires very little labor, because both antagonist and herbicide may be applied simultaneously.
- dichloroacetamides of amino-substituted heterocyclic compounds have not been shown to be able to completely eliminate injury to corn by a thiocarbamate herbicide such as EPTC applied at rates of 6 pounds or more per acre.
- a thiocarbamate herbicide such as EPTC applied at rates of 6 pounds or more per acre.
- dichloroacetamides derived from thiazoleamines, oxazoleamines and thiadiazoleamines have not given sustained protection, either when applied to the seed or allowed to migrate through the soil.
- Amides derived from tetrahydrofurfurylamine, aminopicoline, aminochloropyridine, diaminopyridine and furfurylamine have been shown to give protection when used to treat corn seed.
- dichloroacetamides derived from aminoheterocyclic compounds have not fared well as soil-applied antagonists.
- Amides derived from aliphatic amines such as diallylamine and diisopropylamine have given much better performance when applied to the soil.
- all soil-applied antagonists suffer from the lack of a lasting effect. Apparently the concentration of antagonist in the soil diminishes with time until the developing plants are unable to absorb enough to obtain the desired protection.
- Application of dichloroacetamides to the soil at higher rates to assure a lasting effect usually results in plant injury, as these compounds are phytotoxic at higher concentrations.
- the new class of plant protecting antagonists including all which are useful for either soil application or direct application to seeds are the compounds of the group having the general structural formulas: ##STR2## in which R is hydrogen or C 1 to C 4 alkyl, alkenyl or alkynyl, branched or straight chain and R 1 is C 1 to C 3 alkyl, alkenyl or alkynyl, branched or straight chain, with the total number of carbon atoms in R and R 1 being less than six and preferably less than four, on compounds with both R and R 1 substituents.
- the compounds numbered 1 and 4 are particularly outstanding for use in protecting rice from alachlor.
- the compounds used as starting materials may be obtained from commercial sources or are readily prepared by means of published procedures. Suitable procedures appear, for example, in the following sources: Kubo, H.; Sato, R.; Hamura, I. and Ohi, T. J. Ag. Food Chem., v. 18 p. 60(1970) Lalezari, I. and Sharghi, V. J. Heter. Chem. v. 3 p. 336 (1966) Hurd, C. D. and Wehrmeister, H. L. J. Am. Chem. Soc. v. 71 p. 4007 (1949). Specific synthesis procedures are exemplified below for illustrative purposes.
- herbicides against which plants are protected include alachlor, butylate, cycloate, pebulate, N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ether, diallate, dicamba, dinitramine, N-[3[(1,1,1-trifluoromethylsulfonyl)amino]-4-methylphenyl] acetamide, EPTC, molinate, oxadiazon, perfluidone, propachlor, vernolate and CDEC.
- crops that are protected are rice, corn, barley, wheat, oats and grain sorghum.
- These antagonists may be applied in many known ways: as seed treatments, as soil applied protectants, or by seed soaking.
- the seed treatments may be applied dry, as slurries, or as furrow sprays.
- the soil treatments may be made over the entire field or to small portions of the field. They may be applied as sprays, dusts or granules. The following examples are presented by way of illustration.
- a result scored 5-5-1 would be indistinguishable from EPTC treated checks and a 5-0-5 would be like an untreated check on which there was neither herbicide nor protectant.
- Example 1 Three weeks later the plants are scored as in Example 1.
- the herbicide antagonists of this invention must be applied in an effective amount, sufficient to improve the resistance of the plants to pre-emergent herbicides.
- the skilled worker in the art will be able to determine what is an effective amount by examination of the data in the illustrative examples. It will be readily understood that application to seeds requires a smaller amount of antagonist. The use of excessive amounts is uneconomical and accomplishes nothing beneficial. However, accidental application of an excessive amount, as for instance by overlapping of sprayed areas does not result in reduction of the number of emerging plants or the appearance of pre-emergence herbicidal effects.
- the substantially nonphytotoxic character of these herbicide antagonists is unique and contrasts sharply with the characteristics of the dichloroacetamides. Compounds numbered 1, 2, 6 and 7, as shown in the foregoing table, gave perfect scores in protecting corn from EPTC even when applied to soil at rates as high as 8 lb. per acre.
- the herbicide antagonists of this invention are effective against various types of pre-emergent herbicides.
- Commercial herbicides have been used in the illustrative examples so as to demonstrate practical utility.
- Thiocarbamates and dithiocarbamates are probably the most numerous and readily available of the commercial pre-emergent herbicides and these appear most often in the examples.
- efficacy against a substituted oxadiazolinone (oxadiazon) and a chloroacetanilide (alachlor) are also demonstrated. It is not intended to limit the method of protecting crop plants to protection against only the herbicides of the illustrative examples.
Abstract
New compounds which are herbicide antagonists that are useful for protection of plants from various herbicides are members of the group having the general structural formulas: ##STR1## in which R is hydrogen or C1 to C4 alkyl, alkenyl or alkynyl, branched or straight chain, R1 is C1 to C3 alkyl, alkenyl or alkynyl, branched or straight chain, with the total number of carbon atoms in R and R1 being less than six, preferably less than four, on compounds with both R and R1 substituents. The novel plant protection agents may be applied both to seeds and to the soil.
Description
Amides of dichloroacetic acid derived from a large number of amines are known to be useful as herbicide antagonists to protect plants from pre-emergent thiocarbamate herbicides, as disclosed in U.S. Pat. Nos. 4,021,224 and 4,033,756. Plant protecting antagonists have been used commercially in two ways, (1) by application to the crop seeds at, or prior to planting, so as to assure that antagonist is present when the seeds germinate and begin to grow, or (2) by application to the soil, so that if pre-emergent herbicide in the soil reaches the crop seeds, the antagonist will also be present and will protect the germinating and growing plants. The second method is not as controllable as the first method. Diffusion of the antagonist in the soil may be at a different rate from the diffusion rate of the herbicide and the difference may be dependent upon weather and soil type. Direct seed treatment is generally more effective and efficient with respect to the use of chemicals. However, application to the soil is very convenient and requires very little labor, because both antagonist and herbicide may be applied simultaneously.
In general, dichloroacetamides of amino-substituted heterocyclic compounds have not been shown to be able to completely eliminate injury to corn by a thiocarbamate herbicide such as EPTC applied at rates of 6 pounds or more per acre. For example, dichloroacetamides derived from thiazoleamines, oxazoleamines and thiadiazoleamines have not given sustained protection, either when applied to the seed or allowed to migrate through the soil. Amides derived from tetrahydrofurfurylamine, aminopicoline, aminochloropyridine, diaminopyridine and furfurylamine have been shown to give protection when used to treat corn seed. However, the dichloroacetamides derived from aminoheterocyclic compounds have not fared well as soil-applied antagonists. Amides derived from aliphatic amines such as diallylamine and diisopropylamine have given much better performance when applied to the soil. However, all soil-applied antagonists suffer from the lack of a lasting effect. Apparently the concentration of antagonist in the soil diminishes with time until the developing plants are unable to absorb enough to obtain the desired protection. Application of dichloroacetamides to the soil at higher rates to assure a lasting effect usually results in plant injury, as these compounds are phytotoxic at higher concentrations.
We have discovered a new class of plant-protecting antagonists which appear to give lasting protection against various herbicides at a variety of application rates, both when applied directly to crop seeds, and when applied to the soil. Although we do not wish to be limited by this theory, there are indications that these compounds are less phytotoxic than the dichloroacetamides and are more resistant to decomposition by soil fungi and bacteria. The new class of plant protecting antagonists, including all which are useful for either soil application or direct application to seeds are the compounds of the group having the general structural formulas: ##STR2## in which R is hydrogen or C1 to C4 alkyl, alkenyl or alkynyl, branched or straight chain and R1 is C1 to C3 alkyl, alkenyl or alkynyl, branched or straight chain, with the total number of carbon atoms in R and R1 being less than six and preferably less than four, on compounds with both R and R1 substituents.
New compounds which are particularly outstanding for their ability to protect developing plants from various herbicides, either when applied to plant seed, or to the soil, are exemplified below:
______________________________________
Compound
No. Structural Formula M.P. (°C.)
______________________________________
##STR3## 95-97
2
##STR4## 146-148
3
##STR5## 89-91
4
##STR6## Oil
5
##STR7## 91-93
______________________________________
The following new compounds are particularly outstanding as plant protectants when applied to the soil:
______________________________________
Compound
No. Structural Formula M.P. (°C.)
______________________________________
##STR8## 118-121
1
##STR9## 95-97
2
##STR10## 146-148
3
##STR11## 89-91
4
##STR12## oil
5
##STR13## 91-93
7
##STR14## 91-93
______________________________________
Other new compounds which are outstanding for use as direct seed treating agents are the following:
______________________________________
Com-
pound
No. Structural Formula M.P. (°C.)
______________________________________
##STR15## 103-105
9
##STR16## 118-121
1
##STR17## 95-97
2
##STR18## 146-148
4
##STR19## oil
______________________________________
The compounds numbered 1 and 4 are particularly outstanding for use in protecting rice from alachlor.
Scheme 1 gives a generalized method of synthesis for this class of compounds. ##STR20##
Scheme 2 gives the specific synthesis for compound No. 6, 2-dichloroacetylimino-3-methylthiazol-4-ine. ##STR21##
The compounds used as starting materials may be obtained from commercial sources or are readily prepared by means of published procedures. Suitable procedures appear, for example, in the following sources: Kubo, H.; Sato, R.; Hamura, I. and Ohi, T. J. Ag. Food Chem., v. 18 p. 60(1970) Lalezari, I. and Sharghi, V. J. Heter. Chem. v. 3 p. 336 (1966) Hurd, C. D. and Wehrmeister, H. L. J. Am. Chem. Soc. v. 71 p. 4007 (1949). Specific synthesis procedures are exemplified below for illustrative purposes.
To a solution of 20 g (0.2 m) of 2-aminothiazole (Aldrich Chemical Co.) in DMF (dimethylformamide) (50 ml) was added 35 g (0.25 m) of methyl iodide and the solution stirred at room temperature for 72 hrs. Upon the addition of ethyl acetate, the product crystallized and was collected, giving 44 g, m.p. 185°-187° C.
To a suspension of 4.0 g (0.017 m) of 2-imino-3-methylthiazol-4-ine hydroiodide in THF (tetrahydrofuran) (100 m) was added 5 g of triethylamine. After stirring at room temperature for a few minutes, 2.0 g (0.018 m) of dichloroacetyl chloride was added and stirring was continued for an additional 4 hours. The precipitated salts were collected by filtration and washed with portions of THF, then the filtrate was concentrated to near dryness at reduced pressure. Water was added and the resulting mixture was extracted with ethyl acetate, which was removed at reduced pressure and the residue was then crystallized with ether. The product, 2-dichloroacetylimino-3-methylthiazol-4-ine, was collected and gave 2.0 g, M.P. 118°-131° C.
These antagonists can be useful for reducing the herbicidal injury to many crop plants. Examples of herbicides against which plants are protected include alachlor, butylate, cycloate, pebulate, N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ether, diallate, dicamba, dinitramine, N-[3[(1,1,1-trifluoromethylsulfonyl)amino]-4-methylphenyl] acetamide, EPTC, molinate, oxadiazon, perfluidone, propachlor, vernolate and CDEC. Examples of crops that are protected are rice, corn, barley, wheat, oats and grain sorghum.
These antagonists may be applied in many known ways: as seed treatments, as soil applied protectants, or by seed soaking. The seed treatments may be applied dry, as slurries, or as furrow sprays. The soil treatments may be made over the entire field or to small portions of the field. They may be applied as sprays, dusts or granules. The following examples are presented by way of illustration.
Method: 0.60 g chemical is ground with 4.0 ml of a surfactant mixture (composed of 3 parts Emulphor EL-300, 1 part kerosene and 1 part xylene). An aliquot containing 10.4 mg (2 lb/A) is obtained for antidote assay. This is put in 50 ml H2 O and EPTC is added (41.6 mg or 8 lb/A). The mixture is applied to a 6 in. by 12 in. plastic flat containing soil seeded to 5 kernels of corn.
After three weeks the corn was scored as follows with a three digit code: 5-0-5. The first digit refers to the number of plants emerging. The second number refers to the number of plants distorted by EPTC and the third number refers to the height of the plants. Thus a result scored 5-5-1 would be indistinguishable from EPTC treated checks and a 5-0-5 would be like an untreated check on which there was neither herbicide nor protectant.
Results: The chemical compounds numbered 1, 2 and 6 gave ratings of 5-0-5, indicating that complete protection was obtained at the application rates of the procedure described above.
Method: 5.0 g corn seed is treated with the indicated amount (1/8%, 1/2% or 3% by wt.) of chemical in a 3-dram vial. Five small drops (1%) methanol is added and the vial is shaken 20 sec. in a Spex mixer. Five seeds are planted in greenhouse soil in a 6 in.×12 in. plastic flat. 8 lb/A EPTC is applied directly over the seed in 50 ml. water. The seed is covered and the flat is watered.
Three weeks later the plants are scored as in Example 1.
Results: Compounds which gave perfect scores (5-0-5) are as follows:
______________________________________
Treatment rate in % by weight of seed
Compound No. 1/8% 1/2% 3%
______________________________________
1 5-0-5 5-0-5
2 5-0-5 5-0-5
8 5-0-5 5-0-5
9 5-0-5 5-0-5
______________________________________
The compounds disclosed above were employed as plant-protecting agents, both by soil and seed treatment at various application rates, with various herbicides, according to the exemplified procedures. Perfect scores of 5-0-5 which were obtained are tabulated below.
__________________________________________________________________________
Type of
Compound
Application
Number
and rate Crop
Herbicide and rate
Remarks
__________________________________________________________________________
1 1-8 lb/A. on soil
corn
EPTC 8 lb/A.
(preferred use)
1 2 lb/A. on soil
corn
vernolate 3 lb/A.
1 2 lb/A. on soil
corn
molinate 6 lb/A.
1 2 lb/A. on soil
corn
cycloate 4 lb/A.
1 2 lb/A. on soil
corn
ethiolate 3 lb/A.
1 2 lb/A. on soil
corn
ethyl N-2-chloroacetyl-
(Antor)
N-(2,6-diethylphenyl)
glycinate 4 lb/A.
1 2 lb/A. on soil
corn
CDEC 4 lb/A.
(MC-0194)
ethyl 2-methyl-4-chloro-
phenoxythiolacetate
1 2 lb/A. on soil
corn
oxadiazon 4 lb/A.
(Ronstar)
1 1/2% w/w on seed
rice
alachlor 2 lb/A.
(preferred use)
2 1-8 lb/A. on soil
corn
EPTC 8 lb/A.
2 2 lb/A. on soil
corn
vernolate 3 lb./A.
2 2 lb/A. on soil
corn
molinate 6 lb/A.
2 2 lb/A. on soil
corn
cycloate 4 lb/A.
2 2 lb/A. on soil
corn
ethiolate 3 lb/A.
2 2 lb/A. on soil
corn
diallate 4 lb/A.
3 1 lb/A. on soil
corn
EPTC 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
4 1 lb/A. on soil
corn
EPTC 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
5 1 lb/A. on soil
corn
EPTC 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 1/2 to 8 lb/A. on soil
corn
EPTC at 8 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
vernolate 3 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
molinate 6 lb/A.
(antagonist and
herbicide sprayed
as mixutre)
6 2 lb/A. on soil
corn
cycloate 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
pebulate 2 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
ethiolate 3 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
CDEC 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
6 2 lb/A. on soil
corn
diallate 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 1 to 8 lb/A. on soil
corn
EPTC 8 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
corn
vernolate 3 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
corn
molinate 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
corn
cycloate 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
corn
pebulate 2 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
corn
ethiolate 3 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
barley
molinate 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
7 2 lb/A. on soil
rice
molinate 6 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
EPTC 8 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
molinate 6 lb/A.
(antagonist and
hericide sprayed
as mixture)
8 1% w/w on seed
corn
cycloate 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
alachlor 2 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
ethiolate 3 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
CDEC 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
8 1% w/w on seed
corn
diallate 4 lb/A.
(antagonist and
herbicide sprayed
as mixture)
__________________________________________________________________________
The herbicide antagonists of this invention must be applied in an effective amount, sufficient to improve the resistance of the plants to pre-emergent herbicides. The skilled worker in the art will be able to determine what is an effective amount by examination of the data in the illustrative examples. It will be readily understood that application to seeds requires a smaller amount of antagonist. The use of excessive amounts is uneconomical and accomplishes nothing beneficial. However, accidental application of an excessive amount, as for instance by overlapping of sprayed areas does not result in reduction of the number of emerging plants or the appearance of pre-emergence herbicidal effects. The substantially nonphytotoxic character of these herbicide antagonists is unique and contrasts sharply with the characteristics of the dichloroacetamides. Compounds numbered 1, 2, 6 and 7, as shown in the foregoing table, gave perfect scores in protecting corn from EPTC even when applied to soil at rates as high as 8 lb. per acre.
The herbicide antagonists of this invention are effective against various types of pre-emergent herbicides. Commercial herbicides have been used in the illustrative examples so as to demonstrate practical utility. Thiocarbamates and dithiocarbamates are probably the most numerous and readily available of the commercial pre-emergent herbicides and these appear most often in the examples. However, it should be recognized that efficacy against a substituted oxadiazolinone (oxadiazon) and a chloroacetanilide (alachlor) are also demonstrated. It is not intended to limit the method of protecting crop plants to protection against only the herbicides of the illustrative examples.
Claims (9)
1. 2-Dichloroacetylimino-3-methyl-1,3,4-thiadiazol-4-ine.
2. 2-Dichloroacetylimino-3,4-dimethyl-4-thiazoline.
3. 2-Dichloroacetylimino-3,5-dimethyl-1,3,4-thiadiazol-4-ine.
4. 2-Dichloroacetylimino-3-ethyl-1,3,4-thiadiazol-4-ine.
5. 2-Dichloroacetylimino-3-ethyl-5-methyl-1,3,4-thiadiazol-4-ine.
6. 2-Dichloroacetylimino-3-methyl-4-thiazoline.
7. 2-Dichloroacetylimino-3-(2-propynyl)-1,3,4-thiadiazol-4-ine.
8. 2-Dichloroacetylimino-3-methyl-4,5,6,7-tetrahydrobenzothiazoline.
9. 2-Dichloroacetylimino-3-methyl-5-(2-methyl-propenyl)-1,3,4-thiadiazol-4-ine.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/946,975 US4237302A (en) | 1978-09-29 | 1978-09-29 | Dichloroacetylimino herbicide antagonists as plant protection agents |
| US06/137,670 US4279636A (en) | 1978-09-29 | 1980-04-04 | Dichloroacetylimino herbicide antagonists as plant protection agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/946,975 US4237302A (en) | 1978-09-29 | 1978-09-29 | Dichloroacetylimino herbicide antagonists as plant protection agents |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/137,670 Division US4279636A (en) | 1978-09-29 | 1980-04-04 | Dichloroacetylimino herbicide antagonists as plant protection agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4237302A true US4237302A (en) | 1980-12-02 |
Family
ID=25485280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/946,975 Expired - Lifetime US4237302A (en) | 1978-09-29 | 1978-09-29 | Dichloroacetylimino herbicide antagonists as plant protection agents |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4237302A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0047052A1 (en) * | 1980-08-29 | 1982-03-10 | Gulf Oil Corporation | 2-Iodoacetylimino-3-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-ine and use as a fungicide |
| US4437875A (en) | 1980-04-14 | 1984-03-20 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4437876A (en) | 1980-04-14 | 1984-03-20 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4586948A (en) * | 1981-04-22 | 1986-05-06 | Monsanto Company | 2,4-disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4602937A (en) * | 1978-05-15 | 1986-07-29 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4602454A (en) * | 1978-05-15 | 1986-07-29 | Monsanto Company | 2,4-disubstituted-5-thiazole-carboxylic acids and derivatives |
| US5201933A (en) * | 1988-08-01 | 1993-04-13 | Monsanto Company | Safening herbicidal benzoic acid derivatives |
| WO1997000250A1 (en) * | 1995-06-15 | 1997-01-03 | Nissan Chemical Industries, Ltd. | Process for producing 3-(3-fluoropropyl)-2-iminothiazoline |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3523122A (en) * | 1969-02-03 | 1970-08-04 | Parke Davis & Co | Novel 5-nitro-4-thiazolin-2-ylidene compounds |
| US3565901A (en) * | 1969-01-29 | 1971-02-23 | Air Prod & Chem | Certain salts of 1,3,4-thiadiazol-2-ylureas |
| DE2218097A1 (en) * | 1971-04-16 | 1972-11-02 | Stauffer Chemical Co., New York, N. Y. (V.StA.) | Herbicidal agent and its uses |
| JPS496650A (en) * | 1972-03-08 | 1974-01-21 | ||
| US4021224A (en) * | 1971-12-09 | 1977-05-03 | Stauffer Chemical Company | Herbicide compositions |
| US4092148A (en) * | 1970-02-17 | 1978-05-30 | Air Products And Chemicals, Inc. | Amide derivatives of 1,3,4-thiadiazoles |
-
1978
- 1978-09-29 US US05/946,975 patent/US4237302A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565901A (en) * | 1969-01-29 | 1971-02-23 | Air Prod & Chem | Certain salts of 1,3,4-thiadiazol-2-ylureas |
| US3523122A (en) * | 1969-02-03 | 1970-08-04 | Parke Davis & Co | Novel 5-nitro-4-thiazolin-2-ylidene compounds |
| US4092148A (en) * | 1970-02-17 | 1978-05-30 | Air Products And Chemicals, Inc. | Amide derivatives of 1,3,4-thiadiazoles |
| DE2218097A1 (en) * | 1971-04-16 | 1972-11-02 | Stauffer Chemical Co., New York, N. Y. (V.StA.) | Herbicidal agent and its uses |
| US4021224A (en) * | 1971-12-09 | 1977-05-03 | Stauffer Chemical Company | Herbicide compositions |
| JPS496650A (en) * | 1972-03-08 | 1974-01-21 |
Non-Patent Citations (1)
| Title |
|---|
| L. Bambas, Five-membered Heterocyclic Compounds with Nitrogen and Sulfur, (1952), Interscience Publishers, N.Y., pp. 103-104. * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4602937A (en) * | 1978-05-15 | 1986-07-29 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4602454A (en) * | 1978-05-15 | 1986-07-29 | Monsanto Company | 2,4-disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4437875A (en) | 1980-04-14 | 1984-03-20 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| US4437876A (en) | 1980-04-14 | 1984-03-20 | Monsanto Company | 2,4-Disubstituted-5-thiazole-carboxylic acids and derivatives |
| EP0047052A1 (en) * | 1980-08-29 | 1982-03-10 | Gulf Oil Corporation | 2-Iodoacetylimino-3-methyl-5-trifluoromethyl-1,3,4-thiadiazol-4-ine and use as a fungicide |
| US4586948A (en) * | 1981-04-22 | 1986-05-06 | Monsanto Company | 2,4-disubstituted-5-thiazole-carboxylic acids and derivatives |
| US5201933A (en) * | 1988-08-01 | 1993-04-13 | Monsanto Company | Safening herbicidal benzoic acid derivatives |
| WO1997000250A1 (en) * | 1995-06-15 | 1997-01-03 | Nissan Chemical Industries, Ltd. | Process for producing 3-(3-fluoropropyl)-2-iminothiazoline |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1695968C3 (en) | 4-methylthiazolyl-5-carboxanilide compounds, processes for their preparation and their use as fungicidal agents | |
| US4175081A (en) | 5-Substituted thiadiazole ureas | |
| RU2029471C1 (en) | Pyrimidine derivatives, herbicide composition, and a method of struggle against weed using composition | |
| US4237302A (en) | Dichloroacetylimino herbicide antagonists as plant protection agents | |
| PL110714B1 (en) | Method of producing new heterocyclic derivatives containing in ring nitrogen,specially oxazolidine or thiazolidine | |
| US3617252A (en) | Herbicidal dinitro-1,3-phenylenediamine compounds | |
| CA1108618A (en) | 1, 2, 3-thiadiazol-3-in-5-ylidene ureas, a process for their manufacture and their use in regulating the growth of plants | |
| US4279636A (en) | Dichloroacetylimino herbicide antagonists as plant protection agents | |
| US6348614B1 (en) | Aminobutyric acid fungicides | |
| JPS6059901B2 (en) | Substituted cyclopropylmethoxyurea, herbicidal composition, and weeding method | |
| KR830001038B1 (en) | Substituted 1,3 - dithio heterocyclic compounds as herbicidal | |
| US4182712A (en) | 5-Substituted thiadiazole ureas | |
| JPS585161B2 (en) | All the best | |
| JPH02202881A (en) | Benzothiazole derivative | |
| DE69823191T2 (en) | 1,2,3-THIADIAZOLE DERIVATIVES, MEANS FOR CONTROLLING PLANT DISEASES AND METHOD FOR THE USE THEREOF | |
| US4188203A (en) | Herbicidal and phytohormonal amidoximes | |
| US3356724A (en) | Herbicidal alpha-halo-nu-cyclohexyl-acetamides | |
| US3497343A (en) | Method of stunting plant growth with substituted hydrazonium salts | |
| US3617250A (en) | Herbicidal trifuluoromethyl-1,3-phenylenediamine compounds | |
| US4187097A (en) | N-hydrazides of 2-benzothiazolinone as plant growth regulants | |
| US4599424A (en) | 5-substituted thiadiazole ureas and their use as herbicides | |
| US3873300A (en) | Dithiocarbamate hydrochloride salts as herbicides | |
| US5087284A (en) | 5-substituted thiadiazole ureas and their use as herbicides | |
| RU1797459C (en) | Method of selective struggle against weeds in cereals | |
| US3903153A (en) | Dithiocarbamate hydrochloride salts and their manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A COR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CHEVRON U.S.A. INC.;REEL/FRAME:004688/0451 Effective date: 19860721 Owner name: CHEVRON RESEARCH COMPANY,CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CHEVRON U.S.A. INC.;REEL/FRAME:004688/0451 Effective date: 19860721 |
|
| AS | Assignment |
Owner name: CHEVRON U.S.A. INC. Free format text: MERGER;ASSIGNOR:GULF OIL CORPORATION;REEL/FRAME:004748/0945 Effective date: 19850701 |